Low fluid loss composition



Jan. 29, 1957 J. BROWN ET AL 27 LOW FLUID r.oss COMPOSITION Filed April 18, 1956 2 Sheets-Sheet 2 O0. OO

JACK L. BROWN MARY M. LANDERS IN VENTORS. BY

ATTORNEYS LOW FLUID LOSS COMPOSITON Jack L. Brown, Ponca City, Okla., and Mary M. Landers, Dallas, Tex., assignors to Continental (lil Company, Ponca City, Okla., a corporation of Delaware Application April 18, 1956, Serial No. 579,049

25 Claims. (Cl. 252-855) This nvention relates to the treatment of fluids used in well working operations such as drilling and hydraulic fracturing. This application is a continuation-in-part of our copendng application entitled Low Liquid Loss Fluds, Serial No. 464,624, filed October 25, 1954, now abandoned.

In the art of fracturing oil and gas wells, a special fiuid composition (usually called fracturing fiuid) is pumped down the well into contact with the formation to be fractured, and the pressure of the fiuid composition is increased untl the formation is fractured by hydraulic pressure. It is then usually desirabie to incorporate a propping material, such as sand, in the fracturing fiuid, whereby the propping material is carried into the fracture with the fracturng fiuid. After the fracture has been extended to the extent desired, the pressure in the well bore is decreased and the fracturing fiuid flows back into the well bore. At least a portion of the propping material is deposited in the fracture for maintaining the fracture open and enhancing the flow of formation fluids through the fracture into the well bore.

The type of fracture obtained is dependent primarily upon the penetrating characteristics of the fracturing fiuid. That is, a low penetraton fiuid usually gives a vertical fracture (ordinarily the most desirable), and a high penetrating fracturing fiuid usually gives a horizontal fracture (frequently along weak bedding planes in the formation, which is undesirable). Therefore, a primary concern in the art has been to reduce the penetrating characteristcs (usually called the fiuid loss) of fracturing fiuids. Another consideration in the manufacture of fracturing fluids is viscosity. Some operators desire a high viscosity fracturing fiuid, and others desire a low viscosity fracturing fiuid. Therefore, it is highly desirable from an economical point of view that the same basic fracturing fiuid can be readily adapted to either a high or low viscosity fiuid.

Many attempts have been made to solve these problems of the art, and partcularly the reduction of the fiuid loss of fracturing fluids. The usual solution is to incorporate a large quantity of oil-insoluble materials, such as blown asphalt and rubber, in an oil carrier for literally plastering the face of a formation by an accumulation of the plastering material. These large amounts of plastering materials require correspondingly large amounts of dispersing agents and gelling agents to mantain the plastering materials in suspension under the various operating conditions. Fracturing fluds made in this manner undoubtedly attain good fiuid loss properties, but the cost thereof is unnecessarily high and fiuid invariably has a high viscosity. Also, the plasterng materials heretofore used have relatively large particle sizes, thereby necessitating a large amount of the materal to effectvely seal a formation face.

Similar concepts have been used in making drilling fluids.

A recent development in the art of making fracturing atent fluids and fracturing fiuid addtives is shown in United States Patent No. 2645,291, issueci to Vandeveer Voorhees on July 14, 1953. This patent teaches the production of a fracturing fiuid using a hydrocarbon carrier with finely divded oil-insoluble solids suspended in the carrier. The solids range in size from to 400 mesh and from .5 to 10 pounds of the solids are ncorporated in each gallon of fracturng fiuid to obtain a high final viscosity.

The present nvention contemplates a well-working, fiuid composition (such as used in fracturing and drilling operations) using a greatly reduced amount of oil-insoluble solids, as compared to the amounts required in prior compositions. We contemplate using only a small amount of the solids, with a substantial portion of the solids having a particle size less than 2 microns, whch, in cooperation with a minor amount of agglutnant, form a substantially fiuid mpervious seal on the face of a formation. The small amountof solids used requires a correspondingly small amount of a dispersing agent to maintain the solids in suspenson in an oil carrier, and, in some ols, no dispersng agent is required. Furthermore, the present basic compostion has a relatively low viscosity, whch can be increased as desired by merely adding the presently well known gelling agents.

An important object of this nvention is to provide an economical well-working, low fiuid loss composition.

Another object of this nvention is to provide a basic low fiuid loss composition having a low viscosity, wherein the viscosity may be easily increased as desired.

A further object of this nvention is to provide a 10W fiuid loss composition containing only a minor amount of solid material.

A more general object of this nvention is to facilitate and economize well-werking operations.

Another specific object of this nvention is to provide a low fiuid loss composition comprising an oil carrier and only a minor amount of addtive for reducng the fiuid loss properties of the composition.

Other objects and advantages of the nvention will be evident from the following description, when read in conjunction with the accompanying drawings, whch illustrate our nvention.

In the drawings:

Figure 1 is a curve illustrating the fiuid loss properties of a composition produced in accordance with this mventwn.

Figure 2 is a curve similar to Fgure 1 using a difierent low fiuid loss composition.

Stated broadly, the present nvention may be defined as a method of sealing a poreus subsurface formation traversed by a well bore whch comprises depositing on the faces of the formation with whch liquds in the well bore have contact, a layer of finely divided solids wherein the portion of sad layer adjacent the formation comprises solid particles, about 35 percent of which vary in a sze from 005 to 2 microns, and co-depositing with the sold a gelatinous triaterial serving as an agglutinant.

Before proceedng with specific examples illustrating om nvention, it may be well to indicate in general the nature of the materials requred in the process.

PETROLEUM OIL The petroleum oil whch may be used as the carrier or vehicle in our irnproved fracturing and drilling fiuid may be substantially any petroleum hydrocarbon liquid. For example, we may use crude oil which is normally available in the vncinity of the well-werking operaton. Such crude ols range in viscosity from 5 to 100 centipo1ses, but nsually between 15 to 25 centipoises taken at a temperature of 70 F. In addition, refined petroleum products may be used, such as kerosene, pale oil, diesel fuel, fuel oil, etc.

OIL-INSOLUBLE SOLIDS OILSOLUBLE DSPERSING AGENT A variety of oil-soluble, ionic surface active agents may be used as the dispersing agent in the process of this iuvention. The sulfonates, sulfates, phenolic compounds, organic p'hosph0rus compounds, phosphorus sulfide treated olefins, and metal soaps of carboxylic acids are typical anionic surface actve agents.

Sulfonates Sulfonates which are suitable are oil-soluble and includc the alkali metal and alkaline earth metal soaps of akyl sulfonic acid, alkaryl sulfnic acid, and the so-called mahogany or petroleum sulfonic acids, and the like. The mahogany soaps include particularly the oil-soluble aromatic sulfonates from petroleum. Many of the aromatic sulfonates have cycloalkyl (i. e. naphthenic) groups in the side chains attached to the benzene ring. The mahogany soaps may include nonaromatic sulfonates produced in conventional sulfuric acid refining of lubricating oil distillates and from the industrial use of fuming sulfuric acid in the refining of petroleum. The industrial production of oil-s0luble mahogany sulfonates trom petroleum is well understood in the art and is described in the literature. Normally, the alkyl sulfonates require about 24 carbon atoms for oil solubility. The alkaryl sulfonates, however, require an alkyl portion totalling only about 18 carbon atoms. T0 attain the requsite oil solubility, therefore, requires that the hydrocarbon portion of the sulfonate have a molecular weight between about 350 and 1,000. Preferably this molecular weight is between 400 and 700. Particularly useful sulfonates include the alkali and alkaline metal diwaxbenzene sulfonates, diwaxtoluene sulfonates, and polydodecylbenzene sulfonates. The wax used in making the wax aromatic sulfonate is obtained from different sources of crde petroleum oil. Various grades of paraffin wax are made With different melting points. The 126128 F. (52.253.3 'C.) melting point wax is a mixture of organic c0mpounds with the molecular weight averging in the range of 330-340. The average carbon content of this mixture of organic compounds will be arouud 24.

Other sulfonates which may be used in the process of this iuvention include, for example, monoand poly-wax substituted naphthalene sulfonates, diphenyl ether sulfonates, naphthalene disulfide sulfonates, diphenyl amine sulfonates, diluryl beta-naphtho-l sulfonates, dicapryl nitro-naphthalene sulfonates, unsaturated parafln wax sulfonates, hydroxy subsituted paraffin wax sulfonates, tetra-amylene sulfonates, monoand poly-chlorosubstituted paraflin wax sulfonates, nitrosoparaffin wax sulfonates; cycloaliphatic sulfonates such as laurylcyclo-hexyl sulfonates, monoand poly-wax substitutcd cyclo-hexyl sulfonates, and the like. The expression petroleum sulfonate is intended to cover all sulfonates derived from petroleum products.

A preferred oilsoluble sulfonate is the product produced by neutralizing postdodecylbenzene overhead sulfonic acid With sodium hydroxide or other base. PDB overhead sulfonic acid is the acid produced by su.lfonating 4 PDB-OH Physical proporties of PDB-OH before sulfonating are as follows:

Phenolic c0mpounds T he phenolic organic comopunds which may be used are the free oil-soluble phenolic compounds or the metal phenates thereof. Oil-solubility is imparted to such phenolic compounds by the presence in the molecule of at least nine aliphatic carbon atoms. Specific examples are: 3,5,5 trimethyl n hexyl phenol, n-decyl phenols, cetyl phenols, nonyl phenols, and the like; alkaryl substituted phenols such as alkyl-phenyl phenols; polyhydroxy alkyl-aromatic compounds such as 20-carbon alkyl resorcinol, or polyhydroxy alkyl-benzenes, such as, for example, octyl catechol, tri-iso-butyl pyrogallol, and the like; mono-hydroxy alkyl-haphthalenes such as 12 carbon alkyl alpha napht'nol, and the like. Alkyl substituted phenol sulfides containing at least 5-alkyl carbon atoms such as iso amyl or nonyl phenol disulfide and the like may be used.

Organc phosphrus compounds Useful o'rganic phosphorus compounds include triand penta-valent organic phosphorus acids and the corresponding thiophosphorus acids and their oil-soluble salts, as, for example, phosphoric acds and thiophosphoric acids, phosphinic acids and thiophosphinic acids, and the like and the oil-soluble salts thereof. The organc radi cals substituted may be aliphatic, cycloaliphatic, aro matic, substituted aromatic, and the like and preferably contain a total of at least about 12 carbon atoms. Suitable phosphoric acid compounds include, for example, mono-wax phosphorus acids, mono-octadecyl phosphorus acid, mono-dodecyl phosphorus acid, methyl cyclohexyl phosphite, capryl phosphite, dicapryl phosphite, zinc monowaxbenzr;ne phosphonate, zinc dodecylbenzene phosph0nate, and the like. Useful.organic thiophosphorus acds iuclude dicapryl dithiophosphoric acids, dilauryl dthiophosphoric acids, di-(methyl, cyclohexyl) dithiophosphorus acids, lauryl monothiophosphoric acids, diphenyl dithiophosphorc acids, ditolyl monothophosphoric acids, d-(iso-propyl-phenyl) monothiophosphoric acids, and the like, and the oil-soluble salts thereof.

Phosphorus sulfide treated olefins The phosphorus sulfide treated olefins and their oilsoluble metal salts which are suitable for use include those customarily used in lubricating oil formulations as corrosion inhibitors and/Or detergents. Specifically, thcy include the potassiurn-polyisobutylenephosphorus sulfide products described by U. S. Patent 2,316,080 issued on April 6, 1943, to Loane and Gaynor and a similar material containingno metal made by addition of a phos phorus sulfide to wax olefins as described in U. S. Patent 2516,119 issued on July 25, 1950, to Hersh. This latter prferred material is made by first forming wax olefins from parafin waxes by halogcnation and dehyclrohalo genation and subsequentlytreating the ole fins wiih a hosphorus sulfide, preferably phosphorus pentasulfide.

Metal soaps of carboxylzc acds Examples of specific soaps which are preferred foi use because of cost and availablity include metal soaps of naphthenic acids and the higher fatty acids.

suitable naphthenic acds nclude substituted cyclopentane monoand di-carboxylic acids and cyclohexane monoand di-carboxylic acids having at least about 15 carbon atoms for oil solubility, for example, cetyl cyclohexane carboxylicacids, dioctyl cyclopentainecarboxylic acids; and dilauryl deca-hydronaphthalene carboXylic acids, and the like, and oil-soluble salts thereof.

Suitable oil-soluble fatty and radicals include those in whi ch there are present at least about 8 carbonatoms, The bariur n salts of theunsaturated andbranched chain acids being oil-soluble with fewer aliphatic carbon atoms than the saturated acids. Specifi: examples are: 2-ethyl l1exoic acid, linoleic acid, and the like. Substtuted fatty acids which are useful may include chloro-stearic acids, ricinoleic acids, and the like.

Catom'c ol-soluble surface active agents Suitable cationc ol-soluble surface active agents for use in the process of our invention include: a substituted oxazoline, obtainable frorn Commercial Solvents Corporation under the trade name Alkatergl C, 0, and OX; heterocyclic tertiary amine obtainable from Alrose Chemical Company under the trade name Alro amines Ci, 0, and S; a secondary fatty acid amne, obtainable from Armour and Company under the trade name Armeen 2C and 2l-IT; quaternary ammonium compounds of the formula obtairiable from;Armour and Company under the trade name Arquad 20 and 2HT; and a modified cationc agent, obtainable trom Alrose Chemical Company under the trade name Detergent I-160."

AGGLUTINANT In general cationc, anionic and nbnonic agglutinants may 'be used. As nsed herein, and in the appended claims, the term agglutinant may be defined as an oilinsoluble surface active agent which, when dispersed in ol, will form a gelatinous precpitate in the presence of a small amount of water. This will iriclude straight chain compounds containing from 5 to 24, preferably5-l8 carbon atbms, and branchled chain compounds containing from 5 to 18 carbon atoms. Particularly elec'tive ag glutinants include; sodum caproate, sodum oleate, sodium stearate, sodiumdodecylbenzene sulfonate and sodium pelargonate. Sodium dodecylbenzenesulfonate is the final product produced by sulfonting DB followed by neutralization with sodum hydroxide. Physical properties of DB a.re as follows:

Specific gravity at 16 C 0.8742

We may also use polyethylene oxide derivativs of 6 alcohols, fatty acids, amnes, amides, and phenols having an amount of ethylene oxide to solubilize the derivative in water. Generally spea.king, the alcohol fatty acid, amine, amide, or phenol may be reacted with about 1 to 2.5times its weight of ethylene oxide to obtain. a

hydrophylic oil-insoluble surface active agent which will form a gelatinous precipitate in the presenceof a small amount of water.

Probably the most important consideration in the preparation of a fracturing or drillng fluid in accordance with this invention is the particle size of the oil-insoluble solids. We have found that the objectives of this invention are attained by dspersing a minute qu antity of a finely divided ol-insoluble solid in a petroleum o.l. As to size (largest dimension of the particle), the partcles may range trom 0.005 te 2 microns. Generally, we prefer to use particles the sizes of which may vary over a somewhat more limited range, namely 0.01 to 2 microns. It is not necessary, however, that the dspersed solid consist entirely of particles having sizes within these limits, as a suitable low fluid loss composition can be prepared wherein all or only a part of the dispersed solids consist of particles the sizes of which vary within the foregoing limits. A product of the latter category is preferred, as such a product is more economical and is available in greater quantities than the former. Regardless of which product is used, we have found that a satisfactory low fluid loss composition is obtained by using a suflicient quantity of the solid to give a composition having a concentration of at least .0025 pound of particles the sizes of which fll within either of the foregoing size limitations per gallon of oil. Generally, we prefer to use a quantity of solids such that the concentralion of particles within eitherof the foregoing size limitations is about .05 pound per gallon of ol. erally speaking, the total amount of solid used should not exceed .20 pound per gallon of oil, with at least .0025 pound of the solid (and preferably about 35 percent of the solid) having a particle size from .005 to 2 microns. This amount of solid provides an economical composition having goed fluid loss properties, and the viscosity of the composition is not unduly high.

Either watersoluble or waterinsoluble finely divided oil-insoluble solids may be used. However, we prefer water-soluble solids since they are easly removed from the well, as by water-washing, if such a result is desirable.

The following exarnples (Tables I and 11) illustrate the marked effect of particle size on the fluid loss properties of a fractnring fluid. In each example, 1.44 grams of ball-milled sodum sulfate or calcium chloride was suspended in 200 cc. of kerosene by the use of 0.72 gram of sodum postdodecylbenzene sulfonate. Each suspension was mixed for 10 minutes with a common malt mixer and then all-owed to settle in a glass tube to determine the. particle size of the solid particles by means of Stokes law. cc. of the suspension containing the desired particle sizes was selected for each of the tests, and

0.12 gram of sodum -dodecylbenzene sulfonte added to the selected suspension. The selected suspension was then mixedfor an additional 10 minutes to disperse the sodum dodecylbenzene sulfonate, andthe fluid loss of the suspension was dctermned by the Standard Field Procedure for Testing Drilling Fluids, Section IV, A. P. I. Test RP29, May 1950, using No. 987 Baroid filter paper.

'IABLE I [Dspersed solid-sodum sulfate] Slze Range (microns) Fluld Loss (cc.l20 min.)

Each of these samples also contained a minnte qnantity of kerosene.

Gen-

T ABLE I.I [Dlspers ed solid-calcium chloride] Each of these samples also contained a minute qufantity of finer solids, butgsu bstantially less than 0025 pound/gallon of kerosenc.

From Tables I andll, it will be observed that the use of.solid particles less than 2 microns in size materially decreases the fluid loss of a fracturng flud. Mny similar tests have been run with the other preferred il-insoluble solids described above in the section Oil-iusoluble solids nd ,in eac h instance, comparable results were obtained. Althugh the solid p'articles in the examples of Tables I and II (which gave the best fluid loss properties) were all inthe size range of frorn 0.005 to 2 microns, it will be understood that substantially the same results are obtined when the solid also comprises larger particles along with the fine particles. Such an exmple is illustrated in TableH1, where the test was run in substantally the Same manneras prevously described.

TABLE III [Dlspersed solid-calcium chloride] Only a suflicient amount of oil-soluble dspersing agent treed be used to dsperse the oil-insoluble solids in the petroleum oil. We have found that trom about 015 to .08jpound of dispersing agent per gallon of petroleum oil is suflicient. A larger amount of dispering agent, up to one pound per gallon or even higher, may be used. However, these larger amounts are not desirable since the costof the fracturing or drillirg fluid is ncreased, and no increased benefits are obtained.

In the event the petroleum oil beng used contains a naturally occurring or previously incorporated l-soluble disper'sing agent, the amount of oil-soluble dispersng agent added to adapt the oil to a fracturing or drilling fluid may be proportionately reduced. In sme oils, the oilslluble dispersi1g agent may be dispensed with entirely.

;It has been found that only from .01 to .08 pound of oil-insluble surface active agent (agglutinant) per gallon of petroleum oil is required to produce a satisfactory low liquid loss fluid.

Specfic examples of variatio'ns in the relative amounts pf oil-sluble dispersing agents and agglutinants are illustratedin Figs.1 and 2. The curves of Figs. 1 and 2 were obtained by runnng the stndard fluid loss test identfied above, usng kerosene as the petroleum oil and a total of0.2 poundof additive per gallon of kerosene, with 50% of the additive being.sodiurn sulfate (as the finely divided solid) in eac h run. In Fig. 1, the il-soluble dispersing agent was sddim naphthenate havng a molecular weight of 320, and the agglutinant was sodium stearate, with theamounts of naplithenate and stearate beng varied as indicated at the bottom of the figure. Since a fluicl loss of 10 cc. or less isconsidered excellent, it will be observed that in this specific example the oil-soluble dispersing agent varied from 19% (019 1b.) to 52% (.052 115.), and the agglutinant varied f rom 48% (048 1b.) to 81% (.081 1b). It will also be noted that the agglutinar1t alone gave a fluid loss of.about 60 cc. j

Similar results are shownirr Fig.2 where the oil-soluble dispzgr sng agent was again so diurn naphthenate (yarying lf rqm;25%(.025 1b.) to 50% (.050 lh.)). n dthe aggluto 2 microns.

ti naut was sodiurn olea te (varying from (050 113,) to 75% (1075 lb. ))l The agglutinant alone.gave afluid loss of about 42 cc. Similar tests were runu sing an additive-;comprising 50% sodium sulfate (as the finely divided solid) and 50% agglutinant, along with approximately 0.35% water based on the total weight of the additiveaudthe petroleum oil (kerosene). In the lastmentioned tests, sodium dodecylbenzene sulfonate as the agglutinant gave a standard fiuid loss of about 12 cc. and sodium lauryl sulfate as the agglutinant gave a standard fluid loss of about 10 cc.

We have foundthat the viscosity of the low fluidloss composition of this irvention varies directly as the amonntof additiveused. Whenthe optimum quantty of the aclditive is used (considerngboth eflectiveness and economics) the viscosity of the fiual composition Will lge less than 50% greater than the original viscosity of the petroleum oil. If the particular operator using the composition desires a higher viscosity fracturing fluid, any desired amount of well known gellng agents may be used, such as sodurn oleate forrned in situ by the addition of oleic acid and then s0dium hydroxide to the predoininaritly oil compositon, as is well known in the art.

A preferred embodiment of this inventon (when used in fracturing) ncludes the use of sodium postdodecyl benzene sulfonate as the oil-soluble dispersing agent; sodium sulfate as the finely divided solid, and soclium dodecylbenzene sulfonate as the agglutinant, with each of these compounds beng in dry form for convenient mixing with a petroleum oil at the site of the well werking operation.

An operable additive, with the required particle size of the finely divided solid, may be obtained by crutching and then evporating the water from a slurry consistiiig of approximately 15% oil-soluble dispersing agent, 30% solid. 5% agglutnant and 50% water. As a specfic example of piparing the preferred additive of this invention, 300 grams of a slurry consisting of 42.4% sodium postdodecylbenzene sulfonate, 5.1% sodum sulfate, 2.5% oil and 50.0% water may be mixed with 97.5 grams of a slurry consisting of 43.5% sodium dodecylbenzene sulfonate, 5.0% sodum sulfate, 0.68% oil and 51.5% water. during mixing and then 234.4 grams of commercial anhydrous sodiurn sulfate are added slowly and the mxing is coutinued for ten minutes. All of the mixing is done at a temperature of C. The slurry obtained by this mixing procedure is then dried on a common drum dryer using a drum temperature of 307 F. speed of 4.2 R. P. M. and steam pressure of p. s. i. The resulting dried product is then ready for use as the preferred additive of thisinvention, and about 35% of the sodium sulfate, when the productis incorporated in a petroleum oil, will consist of particles varying in size frorn about 0.005

The de sired part i cle size may also be obtained by dis solving the solidin a solvent and then dispersing the solution in the oil, as byemulSfication, and then evaporating the solvent. Or by forming a solution of the oxide or hydroxide, dispersing such solution in the oil and then acid treating the mass,as by blowiug with carbon di0Xide, and precipitatingthe fine insoluble solids in situ and removing the solids.

Although we do not wish to be limited to any particular theory, itis beleved that the mechanics or operation of the coinpositin of this invention is such that the oil soluble dispersing agent functionssolely to suspend the finely divded.oildnsoluble solid in the petroleum oil. When the compostion is placed under pressure against a subsurface formation (such as the walls of a well bore), akninof portion of the petroleum oil is nitially forced intothe pores of the formation. As this oil escapes into the.formation a portion of the oil-insoluble solid partclesentersthe. formation pores and become wedged in the pores adjacent ;the formation surface, as, well as 231.6 grams of water are added to the slurries 9 deposited on the surface of the formaton. The agglntinant forms a gelatinous-like layer or blanket on top of and between the deposited solids to provide a barrier at the formation surface which is substantially impervious to further flow of oil into the formation.

Gcnerally speaking, a small amount of water (for example, 0.33% by weight based on the petroleum ol) facilitates the action of the flnid loss composition. It will be observed that this action follows the above-described theory, in that a small amount of water should assist in the preciptation of the agglutinant into a gelatinous-like layer or blanket. However, when an excessive amount of water is used, the agglutinant goes into solution in the water and the effectiveness of the composition is decreased.

As an example of the minute amount of solid required in some oils, 012 pound of the preferred additive of ths invention (which included 60 percent, er 0072 pound of sodium sulfate) per gallon of oil was incorporated in a California crude (known as Turnball crude) and the resulting composition gave a standard flnid loss of cc. when tested as described above. Since about 35% of the solid in the preferred additive consists of particles varying from about 005 to 2 microns, it will be seen that only about 0025 pound of the fine particles (between 005 and 2 microns) was used and a very good flnid loss obtained.

As a practical application of our invention, an oil well was fractured using our low liquid loss flnid. In this test Average Maxi- Maxi- Volume Pro; Iniection rnumsurmum botfractu rduct1on Fracturiug Fluid rato, face prestomhole 1m? flnid, mercase, bbls. sure, pressu re, gallons Percent min. p. s. 1. p. s. 1.

Low Liquid Loss Flud of om Invention 3 2, 300 3, 665 2,000 600 Conventional Fractu.ring Flucl 2. 5 2, 875 3, 820 5, 000 400 These data demonstrate that only about 40% as much oil is used in our process as is required in theconventional process. Furthermore, the production rate of the well was increased by 600 percent as compared to 400 percent where the well was fractured by the conventional viscous fracturing flnid.

As another practical application of onr invention, an oil well was completed using our low liquid loss flnid as a. drilling mud. In this test, pipe was cemented on top of the pay formation and the conventional drilling mud displaced from the hole. Five hundred barrels of drilling flnid were prepared by mixing 0.2 pound of an additive (prepared by mixing 3 parts of sodium postdodecylbenzene overhead sulfonate, 1 part of sodium dodecylbenzene sulfonate and 6 parts of sodium sulfate) per gallon of crude oil. This drilling flnid had a flnid loss of 3 cc. as determined in accordance to the Standard Field Procedure for Testing Drilling Fluids, Section IV, API Test RP29, May 1950. It was used successfully to drill the cement plug and complete the well to total depth.

No trouble was experienced in the drilling operation and on completion, the well came in readily without the 10 necessity of stimulation procedures. The use of the new drilling flnid thereby eliminated several days of drilling rig time which are ordinarily required in swabbing opera tions to bring in oset wells which were drilled using 5 conventonal water base drilling muds.

The flnid loss data listed below were determned in accordance to the Standard Field Procedure for Testing Drilling Fluids, Section IV, API Test RP29, 1950. In al] examples the total amount of additive used was equal 10 to 0.2 pound per gallon of kerosene.

TABLE IV Example Additive 'Fluid loss, m1./30 min.

.A. None 03 0.0' '61b. Na N'aph thenate B 0.0241b. Na Caproate 40 0.10). Na SO 0 076111 Na Naphtheuate-- 0 0.0241b Na 'P l00rg0nate 8 0.101b. N812 SO4.- 0.0761b. Na 'PDBO D 0.02411). Brij 35..---- 11 0.101b. N&2SO4

Brij 35 is the trade name of a condensation product of lauryl alcohol and ethylene oxide obtainable from the Atlas Powder Company.

In the following exarnples the total amount of the additive used was equal to 0.1 lb. per gallon of kerosene. The testing procedure was the same as that employed in obtaining the data of Table IV.

TABLE V S0 nm Na DB Fluid Solizl PDB OH Snlfoate, Sold, Loss, Sulfo ate, Percent Percent rul/30 Percent min.

M1ea 42 28 30 16 o 30 20 50 43 'Iuf Plug 30 20 50 0 0. 42 28 30 39 Portland Cement 42 29 29 8 5 Do 62 17 21 30 Calcium Acetate. 20 40 16 Barnlm Sulfate 40 20 40 11 So1um Biearbonate 40 20 40 7 Oyster hall 40 20 40 18 ale1um Chloride 40 20 40 35 45 Sollum Sulfate-.- 40 20 40 15 Bentonite 40 20 40 15 Ammonium Nitrate 40 20 40 23 Magnesium Sulfate 40 20 40 11 S0 iium Cn1oride-. 40 20 40 14 San 40 20 40 20 Alumilum 0xicle. 40 20 40 14 Lea/1 Oxde 30 20 50 18 Talc 40 20 40 13 Beutoite 60 10 30 20 S0 lium Carboxy Methyl Cellu- 20 25 15 67 23 10 26 75 18 7 17 40 20 40 15 Blown Asphalt 30 10 15 1 Tut Plu is the trade name for ground walnut halls obtalnable from C erokee Laboratories.

All of the above-mentioned materials were s pecally treated, or their manufacture controlled, so that the par ticle size distribution therein was such that in the quantities used, they contributed the amount or quantity of particles in the range below 2 microns required by this erally eeonomizes and facilitates well-working operations. Changes may be made in the precise compositions and combinations shown in the specific examples without departing from the spirit and scope of the nvention as set forth in the appended claims.

We claim:

1. A"low liquid loss ;composition comprising: a major portion of petroleum oil having dspersed therein; a minor amount of oil-insoluble finely divided solids of such fine ness as to provide at least about .0025 pound per gallon of oil of particles varying in size from about 0.005 te 2 microns; and a minor amount, at least .01 pound per gallon of oil, of an agglutinant.

2. A low liquid loss compositon comprising: a major portion of petroleum oil having dispersed therein; a minor amount, at least 0.0072 pound per gallon of oil, of an oil-insoluble finely divided sold of such fineness that about 35 percent of the particles vary in size from about 0.005 te 2 microns; and a minor amount, at least .01 pound per gallon of oil, of an agglutinant.

3. A low liquid loss composition comprising: a major portion of= petroleum oil having dispersed therein; not more than about .20 pound per gallon of said oil of an oil-insoluble finely divided sold of such fineness as to provide at least about .0025 pound per gallon of oil of particles varying in size from about 0.005 te about 2 microns; and a minor amount, at least .01 pound per gallon of oil, of an agglutinant.

4. .A low liquid loss compostion .comprising: a major portion of petroleum oil having dispersed therein; a minor amount of oil-insoluble finely divided solids of such fineness as to provide at least about .0025 pound per gallon of oil of particles varyng in size from about 0.005 to 2 microns; a minor amount of an ol-solnble dispersing agent suficient to hold said oil-insoluble solids in suspension in the oil; and a minor amount, at least .01 pound per gallon of oil, of an agglutinant.

5. A low liquid loss compostion comprising: a major portion of petroleum oil having dispersed therein; a minor amount, at least 0.0072 poundsper gallon of oil, of an oil-insoluble finely divided sold of such fineness that about 35 percent of the particles vary in size from about 0.005 to 2 microns; a minor amount of an oilsoluble dispersing agent sulficient to hold said oil-insoluble solids in suspension in the oil; anda minor amount, at least 01 pound per gallon of oil, of an agglutinant."

6. A low liquid loss composition comprising: a major portion of petroleum oil having dispersed therein; not more than about .20 pound per gallon of said oil ofan oil-insoluble finely divided sold of such finesness as to provide at least about 0025 pound per gallon of oil of particles varying in size from about 0.005 te about 2 microns; a minor amount of an oil-soluble dispersing agent suflieient'to hold said oil-insoluble solids insuspension in the oil; and a minor amount, at least .01 pound per gallon of oil, of an agglutnant.

7. A composition as defined.in claim 1 characterized further in that the oil-insoluble sold is water-soluble.

8. A composition as defined in claim 1 characterized further in that the oil-insoluble sold is water-insoluble.

9. Acomposition as defined in claim 4 characterized further in that the minimum amount of the oil soluble dispersing agent is .015 pound per gallon of petroleum oil.

10. A composition as defined in claim 4 characterized further in that the amount of dispersing agent is from about 015 to .06 pound per gallon of petroleum oil.

11. A composition as defined in claim 2 characterized further in that a total of 0.2 pound of said finely divided solidper gallonof petroleumoil is"dispersed in "said petroleum oil;

12. A low fluid loss composition comprising a major portion of petroleum oil having dispersed therein; .0025 pound of an ol-insolublefinely divided sold"per gallon 12 of petroleum oil, the szes of the individual particles varying from 0.01 te 2 microns, an oil-soluble dispersing agent for suspending said sold in said oil, and from 0.01 to 0.06 pound of an agglutinant per gallon of petroleum oil.

13. A low liquid-loss additive for petroleum oil comprising a finely divided sold of which 5 parts comprises particles the sizes of which range from 0.005 to 2 microns, at least 1.5 parts of an oil-soluble dirpersing agent, and at least 1 part agglutinant, wherein said finely di vicled sold is obtained by evaporative precipitation from a slurry of water, said sold, said agglutinant and said dispersing agent.

14. A low fluid loss composition comprising a major portion of petroleum oil having dspersed therein 0.1 pound of finely divided sodium sulfate per gallon of petroleum oil, with a sufficient portion of the sodium sulfate particles being less than 2 microns in size to reduce the fluid loss of the composition to less than 44 ces. in thirty minutes as determined by the Standard Field Procedure for Testing Drilling Fluids, Section IV, API Test RP29, May 1950, sodium postdodecylbenzene sulfonate for suspending the sodium sulfate in the petroleum oil, and at least 0.01 pound of sodium dodecylbenzene sulfonate per gallon of petroleum oil.

15. A low fluid loss compostion as defined in claim 14 characterized further in that at least 0025 pound of the sodium sulfate per gallon of oil have a particle size rang ing from 0.005 to 2 microns.

16. A low fluid loss compostion as defined in claim 14 characterized further in that about 35 percent of the sodium sulfate has a particle size ranging from 0.005 to 2 microns.

17. A low fluid loss composition as defined in claim 14 characterized further in that from 0.015 to 0.06 pound of sodium postdodecylbenzene sulfonate per gallon of petroleum oil are used to suspend the sodium sulfate in the petroleum oil.

18. A low fluid loss composition comprising a major portion of petroleum oil having dispersed therein at least 0025 pound of finely divided sodium chloride per gallon of petroleum oil, the size of individual particles of sodium chloride ranging from 0.005 te 2 microns, from 0.015 to 0.06 pound of sodium postdodecylbenzene sulfonate per gallon of petroleum oil, and from 0.01 to 0.06 pound of sodium dodecylbenzene sulfonate per gallon of petroleum oil.

19. A low fluid loss composition comprising a major portion of petroleum oil having dispersed therein 0025 pound of finely divided oil-insoluble sold per gallon of petroleum oil, the size of the individual particles of said sold ranging from 0.005 to 2 microns, from 0.015 te 0.06 pound of a metal soap of a naphthenic acid per gallon of petroleum oil, and from 0.01 to 0.06 pound of sodium stearate per gallon of petroleum oil.

20. In a process of working a well wherein a petroleum oil is forced into the well bore under pressure, the method of sealing subsurface formations traversed by the well bore against loss of appreciable amounts of the said oil to the formations, which comprises incorporatng in said oil an additive containing at least 0.01 pound of an agglutinant per gallon of oil, and a suflcient amount of finely divided oil insoluble sold particles varying from 0.005 to 2 microns in size to reduce the fluid loss of the resulting composition to less than 44 ces. in thirty minutes as determined by the Standard Field Procedure for Testing Drilling Fluids, Secton IV, API Test RP29, May 1950, and contacting the faces of the subsurface formations exposed to the well bore with said oil having said additive incorporated therein.

21. In a processof working a well Wherein a petroleum. oil is forced into the well bore under pressnre,the method of sealing subsurface formations traversed by the well bore against loss of appreciable amounts of saidoilfto the formatons which comprises ncorporating insad agglutnant pei gallon of oil, and at least 0.0025 pound per gallon of oil of finely divided oil nso luble solid partcles varying in size frorn 0.005 te 2 microns, but suficient in amount to reduce the fluid loss of the resulting composition to less than 44 ces. in thirty mnutes as determined by the Standard Field Procedure for Testing Drilling Fluids, Section 1V, API Test RP29, May 1950, and.contacting the faces of the subsurface formations exposed to the well bore with said oil having said additive incorporated therein.

22. In a processf Working a well wherein a petroleurri oil is forcedinto the well bore under pressure, the method of sealing subsurface formations traversed by the well bore against loss of appreciable amounts of sad oil to the formations, whch.comprises incorporating in said oil an additive containing at least 0.01 pound of an agglutinant per gallon of oil, and not morethan about 020 pound per gallon of said oil of a finely dvided oil insolble solid of suchfineness as to provide at least 0.0025.p01111d per gallon of oil of particles varying in size frbm about 0.005 to about 2 mcrons, and contacting the faces of the subsurface formations exposed to the wellbore with said oil having said additive incorporated therein.

23. In a process of werking a well wherein a petroleum oil is forced into the well bore under pressure, the

method of sealing subsurface formations traversed by the well bore against loss of appreciable amounts of said oil to the formations, which comprises incorporatng in said oil an additive containing at least 0.01 pound of an agglutinan per gallonof oil, and not more than 0.20 pound per gallon of said oil of a finely dvided oil nsoluble solid of such fineness that about of the particles vary in sze from about 0.005 te 2 microns, and contacting the faces of the subsurface formations exposed to the well bore with said oil having said additve incorporated therein.

24. In a process of werking a well wherein a petroleum oil is:forced into the well bore onder pressure, the method of sealing subsrface formations traversed .by the well bo1e against loss ofappreciable amounts of said oil to the formations, whch Comprises incorporating in saicl oil an addtive containing at least 0.01 pound of an agglutinant per gallonof oil, at least 0.0025 pound per gallon of oil of finely divided oil soluble solid particles varying in size from 0.005 te 2 microns, but sufiicient in amount to reduce the flud loss of the resultng compositon to less than 44 ces. in thirty minutes as determined by the Standard Field Procedure for Testing Drilling Fluids, Section IV, API Test RP29, May 1950, and a suficient amount of an oil-soluble dspersing agent to hold said solids in suspension in the oil, and contacting the faces of the subsurface formations exposed to the well bore with said oil having sad addtive ncorporated therein.

25. n a process of werking a well wherein a petroleum oil is forced into the well bore under pressure, the method of sealing subsurface formations traversed by the. well bore against loss of appreciable amounts of said oil to the formations, which comprises incorporating in said {oil an addtive containing.at least 0.01 pound of sodium do decylbenzene sulfonate per gallon of oil, at least 0.1 pouncl of finely divided sodium sulfate per gallon of oil, with a sulficent portion of sodium sulfate particles being less than 2 microns in size to reduce the fiuid loss of the resulting composition to less than 44 ccs. in thirty mnutes as determined bythe Standard Field Procedure for Testing Drilling Fluids, Section IV, API Test RP29, May 1950, and a sufi'icient amount of a sodiurn postdodecylbenzene sulfonate for suspending the sodium sulfate in the oil, and contactng the faces of the subsurfacc formatons exposed to the well bore with said oil having said additive incorporated therein.

References Cited in the file of this patent UNITED STATES PATENTS Great Britan Sept. 8, 1937 

1. A LOW LIQUID LOSS COMPOSITION COMPRISING: A MAJOR PORTION OF PETROLEUM OIL HAVING DISPERSED THEREIN; A MINOR AMOUNT OF OIL-INSOLUBLE FINELY DIVIDED SOLIDS OF SUCH FINENESS AS TO PROVIDE AT LEAST ABOUT .0025 POUND PER GALLON OF OIL PARTICLES VARYING IN SIZE FROM ABOUT 0.005 TO 